CN108456794A - It is a kind of to be modified AB using polypyrrole3The method of type hydrogen storage alloy - Google Patents

It is a kind of to be modified AB using polypyrrole3The method of type hydrogen storage alloy Download PDF

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Publication number
CN108456794A
CN108456794A CN201810278953.2A CN201810278953A CN108456794A CN 108456794 A CN108456794 A CN 108456794A CN 201810278953 A CN201810278953 A CN 201810278953A CN 108456794 A CN108456794 A CN 108456794A
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China
Prior art keywords
polypyrrole
alloy
hydrogen storage
modified
type hydrogen
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CN201810278953.2A
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Inventor
黄红霞
肖阳
王成
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Guilin University of Technology
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Guilin University of Technology
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Priority to CN201810278953.2A priority Critical patent/CN108456794A/en
Publication of CN108456794A publication Critical patent/CN108456794A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/023—Alloys based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of AB is modified using polypyrrole3The method of type hydrogen storage alloy.AB is prepared using vacuum induction melting method3Type hydrogen storage alloy after crushing alloy pig, with 60 min of rotating speed 300r/min ball millings, sieves 300 mesh alloy powders.Pyrroles is placed in hydrochloric acid, 0.5 h of constant temperature in 0 DEG C of ice-water bath, and chromium solution is made；Ammonium persulfate is dissolved in hydrochloric acid, 0 DEG C of 0.5 h of constant temperature, and ammonium persulfate solution is made；It is slowly added dropwise in ammonium persulfate solution to chromium solution, the reaction was continued 24 h after being added dropwise, deionized water is added and terminates reaction, stands, filtering is washed with deionized, dry at 60 DEG C, obtains black powder polypyrrole.95 ~ 99 mass parts alloy powders are uniformly mixed with 1 ~ 5 mass parts polypyrrole, the sum of the two mass parts are 100, that is, realize and be modified AB using polypyrrole3Type hydrogen storage alloy.The method of the present invention is simple for process, is conducive to industrialized production.Using polypyrrole to AB3Type alloy is modified, and the corrosion resistance and cycle performance of electrode increase.

Description

It is a kind of to be modified AB using polypyrrole3The method of type hydrogen storage alloy
Technical field
The invention belongs to materials chemistry and electrochemical research fields, more particularly to a kind of to be modified AB using polypyrrole3Type Hydrogen bearing alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08Method.
Background technology
Ni-MH battery is considered to have high-power output, high rate capability, long lifespan, good reliability, nontoxic, memoryless Effect, it is at low cost the advantages that ideal clean energy resource.In the research process of Ni-MH battery, novel anode material is always to pay close attention to Focus.Compared to traditional hydrogen bearing alloy, AB3When cathode of the hydrogen bearing alloy of type as Ni-MH battery, because with perfect Activity function and excellent discharge capacity are to more competitive.The present invention is by adding polypyrrole to AB3Type alloy is changed Property, make it that there is better corrosion resistance and excellent chemical property in Ni-MH battery, is a kind of novel effective method.
Invention content
The object of the present invention is to provide a kind of AB is modified using polypyrrole3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08Method.
The thinking of the present invention：In AB3Type alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08In pass through add polypyrrole As modifying agent to improve the corrosion resistance and chemical property of electrode.
The specific steps are：
（1）AB is prepared by vacuum induction melting method3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08, alloy pig After mechanical crushing, with 60 min of rotating speed 300r/min ball millings, the alloy powder of 300 mesh is sieved.
（2）1.4 mL pyrroles are placed in 250 mL beakers, the hydrochloric acid of a concentration of 1.0 mol/L of 75 mL are added, in 0 DEG C of ice Chromium solution is made in 0.5 h of constant temperature in water-bath；The another salt for taking 4.56 g ammonium persulfates to be dissolved in a concentration of 1.0 mol/L of 25 mL In acid, ammonium persulfate solution is made in 0 DEG C of 0.5 h of constant temperature after dissolving；It is slowly added dropwise in ammonium persulfate solution to chromium solution, drips The reaction was continued 24 h after finishing are added, deionized water is added and terminates reaction, stands, filtering is washed with deionized, and is done at 60 DEG C It is dry, obtain black powder polypyrrole.
（3）By 95 ~ 99 mass parts steps（1）Alloy powder obtained and 1 ~ 5 mass parts step（2）Polypyrrole obtained into Row uniformly mixing, the sum of the two mass parts are 100, that is, realize and be modified AB using polypyrrole3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08。
The method of the present invention process conditions are simple, and production equipment is simple, are conducive to industrialized production.Because polypyrrole has certain resist Corrosive power, using polypyrrole to AB3Type alloy is modified, and the corrosion resistance and cycle performance of electrode increase.
Specific implementation mode
Embodiment 1：
（1）AB is prepared by vacuum induction melting method3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08, alloy pig After mechanical crushing, with 60 min of rotating speed 300r/min ball millings, the alloy powder of 300 mesh is sieved.
（2）1.4 mL pyrroles are placed in 250 mL beakers, the hydrochloric acid of a concentration of 1.0 mol/L of 75 mL are added, in 0 DEG C of ice Chromium solution is made in 0.5 h of constant temperature in water-bath；The another salt for taking 4.56 g ammonium persulfates to be dissolved in a concentration of 1.0 mol/L of 25 mL In acid, ammonium persulfate solution is made in 0 DEG C of 0.5 h of constant temperature after dissolving；It is slowly added dropwise in ammonium persulfate solution to chromium solution, drips The reaction was continued 24 h after finishing are added, deionized water is added and terminates reaction, stands, filtering is washed with deionized, and is done at 60 DEG C It is dry, obtain black powder polypyrrole.
（3）By 99 mass parts steps（1）Alloy powder obtained and 1 mass parts step（2）Polypyrrole obtained carries out equal Even mixing is realized and is modified AB using polypyrrole3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08。
Embodiment 2：
（1）AB is prepared by vacuum induction melting method3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08, alloy pig After mechanical crushing, with 60 min of rotating speed 300r/min ball millings, the alloy powder of 300 mesh is sieved.
（2）1.4 mL pyrroles are placed in 250 mL beakers, the hydrochloric acid of a concentration of 1.0 mol/L of 75 mL are added, in 0 DEG C of ice Chromium solution is made in 0.5 h of constant temperature in water-bath；The another salt for taking 4.56 g ammonium persulfates to be dissolved in a concentration of 1.0 mol/L of 25 mL In acid, ammonium persulfate solution is made in 0 DEG C of 0.5 h of constant temperature after dissolving；It is slowly added dropwise in ammonium persulfate solution to chromium solution, drips The reaction was continued 24 h after finishing are added, deionized water is added and terminates reaction, stands, filtering is washed with deionized, and is done at 60 DEG C It is dry, obtain black powder polypyrrole.
（3）By 97 mass parts steps（1）Alloy powder obtained and 3 mass parts steps（2）Polypyrrole obtained carries out equal Even mixing is realized and is modified AB using polypyrrole3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08。
Embodiment 3:
（1）AB is prepared by vacuum induction melting method3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08, alloy pig After mechanical crushing, with 60 min of rotating speed 300r/min ball millings, the alloy powder of 300 mesh is sieved.
（2）1.4 mL pyrroles are placed in 250 mL beakers, the hydrochloric acid of a concentration of 1.0 mol/L of 75 mL are added, in 0 DEG C of ice Chromium solution is made in 0.5 h of constant temperature in water-bath；The another salt for taking 4.56 g ammonium persulfates to be dissolved in a concentration of 1.0 mol/L of 25 mL In acid, ammonium persulfate solution is made in 0 DEG C of 0.5 h of constant temperature after dissolving；It is slowly added dropwise in ammonium persulfate solution to chromium solution, drips The reaction was continued 24 h after finishing are added, deionized water is added and terminates reaction, stands, filtering is washed with deionized, and is done at 60 DEG C It is dry, obtain black powder polypyrrole.
（3）By 95 mass parts steps（1）Alloy powder obtained and 5 mass parts steps（2）Polypyrrole obtained carries out equal Even mixing is realized and is modified AB using polypyrrole3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08。
Modified alloy is surveyed using LAND5.3B battery test systems and CHI660E electrochemical workstations Examination, it is as a result as follows：
（1）After adding the polypyrrole that mass fraction is 1%, 3%, 5%, the maximum discharge capacity of alloy electrode becomes from 357 mAh/g 355 mAh/g（1% polypyrrole）、352 mAh/g（3% polypyrrole）With 357 mAh/g（5% polypyrrole）, 50 cycle after electric discharge Capacity retention ratio improves.
（2）After the polypyrrole for adding different quality containing, electrode exchange current density is respectively increased from 134 mA/g respectively To 178 mA/g, 171 mA/g, 165 mA/g, while limiting current density also increases.
（3）The corrosion potential of electrode increases after addition polypyrrole, shows that the resistance to corrosion of electrode improves.
Above-described embodiment is in AB3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08Middle addition mass fraction is 1%, 3%, 5% polypyrrole.Since polypyrrole has certain resistance to corrosion, the electrode discharge amount after 50 charge and discharge cycles is protected Holdup improves, and the dynamic performance of electrode also improves.

Claims (1)

1. a kind of being modified AB using polypyrrole3The method of type hydrogen storage alloy, it is characterised in that specific steps：
（1）AB is prepared by vacuum induction melting method3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08, alloy pig After mechanical crushing, with 60 min of rotating speed 300r/min ball millings, the alloy powder of 300 mesh is sieved；
（2）1.4 mL pyrroles are placed in 250 mL beakers, the hydrochloric acid of a concentration of 1.0 mol/L of 75 mL are added, in 0 DEG C of ice-water bath Chromium solution is made in 0.5 h of middle constant temperature；Separately 4.56 g ammonium persulfates is taken to be dissolved in the hydrochloric acid of a concentration of 1.0 mol/L of 25 mL, Ammonium persulfate solution is made in 0 DEG C of 0.5 h of constant temperature after dissolving；It is slowly added dropwise in ammonium persulfate solution to chromium solution, is added dropwise The reaction was continued afterwards 24 h are added deionized water and terminate reaction, stand, and filtering is washed with deionized, dry at 60 DEG C, obtains Black powder polypyrrole；
（3）By 95 ~ 99 mass parts steps（1）Alloy powder obtained and 1 ~ 5 mass parts step（2）Polypyrrole obtained carries out equal Even mixing, the sum of the two mass parts are 100, that is, realize and be modified AB using polypyrrole3Type hydrogen storage alloy La0.85Mg0.15Ni2.64Co0.49Mn0.09Al0.08。
CN201810278953.2A 2018-03-31 2018-03-31 It is a kind of to be modified AB using polypyrrole3The method of type hydrogen storage alloy Pending CN108456794A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862514A (en) * 2015-05-17 2015-08-26 桂林理工大学 Surface modifying method of AB3 type hydrogen storage alloy
CN104923776A (en) * 2015-05-17 2015-09-23 桂林理工大学 Method for surface modification of AB3 hydrogen storage alloy by using aniline
CN104942279A (en) * 2015-05-17 2015-09-30 桂林理工大学 Method for using polyaniline surface modification AB3 type hydrogen storage alloy
CN107159879A (en) * 2017-05-24 2017-09-15 桂林理工大学 One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy
CN107838419A (en) * 2017-12-02 2018-03-27 桂林理工大学 One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862514A (en) * 2015-05-17 2015-08-26 桂林理工大学 Surface modifying method of AB3 type hydrogen storage alloy
CN104923776A (en) * 2015-05-17 2015-09-23 桂林理工大学 Method for surface modification of AB3 hydrogen storage alloy by using aniline
CN104942279A (en) * 2015-05-17 2015-09-30 桂林理工大学 Method for using polyaniline surface modification AB3 type hydrogen storage alloy
CN107159879A (en) * 2017-05-24 2017-09-15 桂林理工大学 One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy
CN107838419A (en) * 2017-12-02 2018-03-27 桂林理工大学 One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy

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Title
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Application publication date: 20180828